PHOSPHORESCENT PtAg2 COMPLEX, PREPARATION METHOD THEREFOR AND USE THEREOF

ABSTRACT

Provided is an ionic type phosphorescent metal complex with a racemization structure, a preparation method therefor and a use thereof. The structure of the complex is [PtAg 2 {rac-(PPh 2 CH 2 PPhCH 2 —) 2 }(C≡CR) 2 (PR′ 3 ) 2 ] 2+ A n−   2/n  or [PtAg 2 {meso-(PPh 2 CH 2 PPhCH 2 —) 2 }(C≡CR) 2 (PR′ 3 )(μ-X)] +   m A m− , wherein R is the same or different and is independently selected from alkyl, aryl, heteroaryl, and heteroaryl aryl; R′ is the same or different and is independently selected from alkyl, aryl, and heteroaryl; the alkyl, aryl, and heteroaryl can be substituted by one or more substituents which are selected from alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, halogenated alkyl, and aryl; X is halogen; A m−  and A n−  are monovalent or bivalent anions; and m or n is 1 or 2. The present invention also relates to an organic light emitting diode, a preparation method therefor and use thereof. The organic light emitting diode prepared by taking the phosphorescent metal complex of the present invention as a luminous layer dopant has high-performance organic electroluminescence and can be applied to panel display.

TECHNICAL FIELD

The present invention relates to the field of organicelectroluminescence, which can be used in the field of full-colorflat-panel displays and illumination. In particular, the presentinvention relates to a PtAg₂ (meso-/rac-dpmppe) heterotrinuclearmetal-organic alkynyl complex for preparing organic light emittingdiodes.

BACKGROUND ART

Organic electroluminescence refers to the phenomenon in which electricalenergy is directly converted into light energy using organic lightemitting diodes (OLEDs) at a low DC voltage in the range of 3V to 12V,which is broadly applied in the field of flat panel displays andlighting. Compared to traditional illumination and display technologies,organic electroluminescence has many advantages such as full-colordisplay, wide viewing angle, high resolution, fast response, low powerconsumption, low temperature resistance, and so on; and organic lightemitting devices have excellent characteristics such as simplestructure, ultra-light, ultra-thin, flexible, foldable, and so on.

The key feature of organic light emitting diodes relies onlight-emitting thin-film materials. At present, most of thephosphorescent materials used in commercial organic electroluminescentdevices are electroneutral cyclometalated iridium (III) complexes, whichare doped into organic host materials to form light-emitting layers. Itsgreatest advantage is that it is easy to fabricate ideal thin-filmlight-emitting layers by vacuum thermal evaporation. However, equipmentrequired for vacuum evaporation is costly and, in particular, processesfor preparing organic doped light-emitting thin-film layers arecomplicated, which greatly limit industrial development and commercialapplications of organic light emitting diodes in large-area full-colordisplays. To break through the above technical bottlenecks, it is afeasible alternative to select ionic-type phosphorescent organometalliccompounds with high quantum efficiency as luminescent materials.Compared to electroneutral compounds, processes for the preparation ofionic-type phosphorescent metal complexes are simpler and cheaper, andthe complexes are more stable, and soluble in organic solvents, whichmake it suitable for fabricating films using large-area solution-basedspin-coating or inkjet printing, thus significantly reducing devicepreparation costs.

DETAILED DESCRIPTION OF THE INVENTION

An object of the present invention is to provide a meso- orrac-ionic-type phosphorescent PtAg₂ complex, a preparation methodtherefor and use thereof.

Another object of the present invention is to provide a luminescentmaterial containing the above ionic-type phosphorescent metal complex,which is used for preparing a high-performance organic light emittingdiode.

The objects of the present invention can be realized by the followingmethod.

An ionic-type phosphorescent metal complex with a racemizationstructure, which is shown in the following formula (I) or formula (II):

[PtAg₂{rac-(PPh₂CH₂PPhCH₂—)₂}(C≡CR)₂(PR′₃)₂]²⁺A^(n−) _(2/n);  (I)

or

[PtAg₂{meso-(PPh₂CH₂PPhCH₂—)₂}(C≡CR)₂(PR′₃)(μ-X)]⁺ _(m)A^(m−)  (II)

wherein,

R is identical or different, independently selected from alkyl, aryl,heteroaryl or heteroaryl aryl;

R′ is identical or different, independently selected from alkyl, aryl orheteroaryl;

the alkyl group, aryl group, or heteroaryl group is optionallysubstituted by one or more substituents, and the substituent is selectedfrom an alkyl group, an alkenyl group, an alkynyl group, an alkoxygroup, an amino group, a halogen, a haloalkyl group and an aryl group;

X is halogen;

A^(m−) or A^(n−) is a monovalent or bivalent anion, and m or n is 1 or2. The anion is, for example, ClO₄ ⁻, PF₆ ⁻, SbF₆ ⁻, BF₄ ⁻, SiF₆ ²⁻,etc. μ stands for bridging.

According to the present invention, the complex of formula (I) has aracemic structure and the complex of formula (II) has a meso structure.

According to the present invention, the stereostructure of thephosphorescent metal complex of formula (I) or formula (II) isrepresented as follows:

In the present invention, the alkyl group is a linear or branched alkylgroup having 1 to 10 carbon atoms, preferably 1 to 6, for example,methyl, ethyl, propyl, n-butyl, isobutyl, t-butyl, etc.

The alkenyl group represents a linear or branched alkenyl group having 2to 6 carbon atoms, for example, vinyl, propenyl, butenyl, etc.

The alkynyl group represents a linear or branched alkynyl group having 2to 6 carbon atoms, for example, ethynyl, propynyl, butynyl, etc.

The aryl group is a monocyclic or polycyclic aromatic group having 6 to20 carbon atoms. Representative aryl groups include phenyl, naphthyl,etc.

The heteroaryl group is a monocyclic or polycyclic heteroaromatic grouphaving 1 to 20 carbon atoms containing at least one, preferably one tofour, of heteroatoms selected from N, S or O. Representativeheteroaromatic groups include pyrrolyl, pyridyl, pyrimidinyl,imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, carbazolyl, quinolyl,quinozolinyl, indolyl, phenothiazinyl, etc.

According to the present invention, A^(m−) or A^(n−) is preferably ClO₄⁻, PF₆ ⁻, SiF₆ ²⁻, etc., and m or n is 1 or 2.

According to the present invention, R is preferably aryl, carbazolyl,phenothiazinyl, or carbazolylaryl. The aryl group, carbazolyl group, orphenothiazinyl group is optionally substituted by one or moresubstituents, and the substituent is selected from the group consistingof alkyl, alkoxy, amino, halogen, haloalkyl, aryl; R′ is preferablyaryl, or nitrogen-containing heterocyclic group (e.g. carbazolyl); thearyl group, or nitrogen-containing heterocyclic group is optionallysubstituted by one or more substituents, and the substituent is selectedfrom the group consisting of alkyl, alkoxy, amino, halogen, haloalkyl,aryl. More preferably, R is phenyl, alkylphenyl, haloalkylphenyl,carbazolylphenyl, carbazolyl, alkylcarbazolyl, phenylcarbazolyl,phenothiazinyl, or alkylphenothiazinyl; R′ is phenyl, alkylphenyl,carbazolyl, alkylcarbazolyl, or phenylcarbazolyl.

According to the present invention, the specific structures of theionic-type phosphorescent metal complexes are preferably represented asfollows:

A method for preparing the phosphorescent complex of formula (I) is alsoprovided by the present invention, comprising the following steps: 1)reacting rac-(PPh₂CH₂PPhCH₂—)₂ with Pt(PPh₃)₂(C≡CR)₂ in a solvent toobtain an intermediate; 2) the intermediate obtained in step 1) reactingwith [Ag(tht)](A^(n−)) and PR′₃ in a solvent to obtain thephosphorescent complex of formula (I), wherein tht istetrahydrothiophene, and A^(n−), R, R′ and X are as defined above.

A method for preparing the phosphorescent complex of formula (II) isalso provided in the present invention, comprising the following steps:A) reacting meso-(PPh₂CH₂PPhCH₂—)₂ with Pt(PPh₃)₂(C≡CR)₂ in a solvent toobtain an intermediate; B) the intermediate obtained in step A) reactingwith PR′₃, ^(n)Bu₄NX and [Ag(tht)](A^(m−)) in a solvent to obtain thephosphorescent complex of formula (II), wherein tht istetrahydrothiophene, and A^(m−), R, R′ and X are as defined above.

According to the present invention, in step 1) and step A), the solventis preferably halogenated hydrocarbon, such as dichloromethane.Preferably, the intermediates obtained in the reaction are concentratedand recrystallized.

According to the present invention, in step 2) and step B), the solventis preferably halogenated hydrocarbon, such as dichloromethane.Preferably, in step B), PR′₃ and ^(n)Bu₄NX are firstly mixed to obtain amixed solution, and then the mixed solution and [Ag(tht)](A^(m−)) areadded to a solution in which the intermediate obtained in the above stepA) is dissolved.

According to the present invention, in the method, a molar ratio ofrac-(PPh₂CH₂PPhCH₂—)₂:Pt(PPh₃)₂(C≡CR)₂:[Ag(tht)](A^(n−)):PR′₃ is1-1.5:1-1.5:2-3:2-3, preferably 1:1:2:2; a molar ratio ofmeso-(PPh₂CH₂PPhCH₂—)₂:Pt(PPh₃)₂(C≡CR)₂:[Ag(tht)](A^(m−)):^(n)Bu₄NX:PR′₃is 1-1.5:1-1.5:2-3:1-1.5:1-1.5, preferably 1:1:2:1:1.

According to the present invention, the reactions are all carried out atroom temperature. Preferably, after completion of the reaction, silicagel column chromatography is used for separation and purification.

The phosphorescent complex of formula (I) or formula (II) of the presentinvention exhibits relatively strong phosphorescence emission in solidand thin films, and the phosphorescence quantum yield of the thin filmsis greater than 50%; moreover, the emission spectrum is relatively broadfrom sky-blue to orange red. Therefore, it can be used as a dopant in alight-emitting layer, which is applied for preparing organic lightemitting diodes.

Use of the phosphorescent complexes in organic light emitting diodes isalso provided in the invention.

Furthermore, an organic light emitting diode, comprising alight-emitting layer, wherein the light-emitting layer comprises thephosphorescent complex of formula (I) or formula (II), is also providedin the present invention.

According to the present invention, in the light-emitting layer, thephosphorescent complex of formula (I) of the present inventionpreferably accounts for 3-20% (percentage by weight) of all materials,more preferably 5-10%. More preferably, 6% by weight of thephosphorescent complex of formula (I) of the invention doped into hostmaterials is used as the light-emitting layer. The phosphorescentcomplex of formula (II) of the present invention accounts for 5-25%(percentage by weight) of all materials, more preferably 8-15%. Morepreferably, 10% by weight of the phosphorescent complex of formula (II)of the present invention doped into host materials is used as thelight-emitting layer.

According to the present invention, the structures of the organic lightemitting diodes may be various known in the prior art, preferablycomprising an anode layer, a hole injection layer, optionally a holetransport layer, a light-emitting layer, an electron transport layer, anelectron injection layer and a cathode layer. The organic light emittingdiodes further comprises a substrate (e.g. a glass substrate). The anodecan be indium tin oxide, and the hole injection layer can be PEDOT:PSS(PEDOT:PSS=poly(3,4-ethyleneoxythiophene)-poly(styrene sulfonate)). Thehole transport layer is CuSCN, CuI, or CuBr. The light-emitting layercontains the phosphorescent complex of the present invention and asubstance having a hole-transport and/or electron-transport property.Herein, the substance having a hole-transport property is one or moreselected from 2,6-DCZPPY (2,6-bis (3-(9H-carbazol-9-yl)phenyl)pyridine),mCP (1,3-bis(9-carbazolyl)benzene), CBP(4,4′-bis(9H-carbazol-9-yl)-1,1′-biphenyl), or TCTA(tris(4-(9H-carbazol-9-yl)phenyl)amine). The substance having aelectron-transport property is OXD-7(1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene); theelectron transport layer is one or more selected from BmPyPB (3,3″,5,5″-tetra(pyridin-3-yl)-1,1′:3′,1″-terphenyl), TPBi(1,3,5-tris(1-phenyl-1H-benzo[d]imidazole-2-yl)phenyl), BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) or OXD-7; the electroninjection layer is LiF, and the cathode layer is Al.

According to the present invention, a device structure containing thephosphorescent complex of formula (I) is preferably ITO/PEDOT:PSS (50nm)/CuSCN (30 nm)/70.5% 2,6-DCZPPY:23.5% OXD-7:6 wt % of the complex offormula (I) of the present invention (50 nm)/BmPyPB (50 nm)/LiF (1nm)/Al (100 nm), or ITO/PEDOT:PSS (50 nm)/70.5% mCP:23.5% OXD-7:6 wt %of the complex of formula (I) of the present invention (50 nm)/BmPyPB(50 nm)/LiF (1 nm)/Al (100 nm); a device structure containing thephosphorescent complex of formula (II) is ITO/PEDOT:PSS (50 nm)/CuSCN(30 nm)/90% 2,6-DCZPPY:10 wt % of the complex of formula (II) of thepresent invention (50 nm)/BmPyPB (50 nm)/LiF (1 nm)/Al (100 nm), orITO/PEDOT:PSS (50 nm)/90% mCP:10 wt % of the complex of formula (II) ofthe present invention (50 nm)/BmPyPB (50 nm)/LiF (1 nm)/Al (100 nm).Herein, ITO is an indium tin oxide conductive film, PEDOT:PSS ispoly(3,4-ethyleneoxythiophene)-poly(styrene sulfonate), 2,6-DCZPPY is2,6-bis (3-(9H-carbazol-9-yl)phenyl)pyridine, mCP is1,3-bis(9-carbazolyl)benzene, OXD-7 is1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene and BmPyPBis 3,3″, 5,5″-tetra(pyridin-3-yl)-1,1′:3′,1″-terphenyl.

A method for preparing the organic light emitting diodes is alsoprovided, the method comprising: 1) fabricating a hole injection layerof the organic light emitting diodes on an anode through a solutionprocess; 2) optionally fabricating a hole transport layer of the organiclight emitting diodes through a solution process; 3) fabricating alight-emitting layer doped with the phosphorescent complexes of thepresent invention through a solution process; 4) fabricating an electrontransport layer, an electron injection layer and a cathode layer insequence through a vacuum thermal evaporation deposition process.

In a preferred embodiment, for the phosphorescent complex of formula(I), the method comprises: firstly, fabricating a hole injection layerby using aqueous PEDOT:PSS; secondly, fabricating a hole transport layerby using a solution of cuprous thiocyanate in diethyl sulfide;furthermore, fabricating a light-emitting layer by doping the blendedhost materials of hole-transport 2,6-DCZPPY and electron-transport OXD-7with the phosphorescent complex of formula (I) of the present invention;and then fabricating a BmPyPB electron transport layer, a LiF electroninjection layer and an Al cathode layer in sequence through a vacuumthermal evaporation deposition process. For the phosphorescent complexof formula (II), the method comprises: firstly, fabricating a holeinjection layer by using aqueous PEDOT:PSS; secondly, fabricating a holetransport layer by using a solution of cuprous thiocyanate in diethylsulfide; furthermore, fabricating a light-emitting layer by dopinghole-transport 2,6-DCZPPY and the phosphorescent complex of formula (II)of the present invention; and then fabricating a BmPyPB electrontransport layer, a LiF electron injection layer and an Al cathode layerin sequence through a vacuum thermal evaporation deposition process.

According to the present invention, in the method, the PEDOT:PSS holeinjection layer and the light-emitting layer doped with 2,6-DCZPPY:OXD-7or 2,6-DCZPPY are, respectively, fabricated using a solution-basedspin-coating method, and the BmPyPB electron transport layer and LiFelectron injection layer are fabricated through a vacuum thermalevaporation deposition process.

The organic light emitting diodes prepared from the phosphorescentcomplexes of the present invention have excellent performance, andrelatively high electrical-optical conversion efficiency.

Use of the organic light emitting diode is further provided, which canbe used in the field of flat-panel displays and daily illumination.

Compared with the prior art, the present invention has the followingadvantages:

-   -   1) The phosphorescent complexes of the present invention exhibit        strong phosphorescence emission in solid and thin films, wherein        the quantum efficiency of the thin films is higher than 50% or        even reaches 90%;    -   2) The organic light emitting devices are assembled by using the        phosphorescent Pt—Ag heterometallic complexes as a luminescent        material for the first time in the present invention, and the        organic light emitting diodes prepared by using the        phosphorescent complexes of the present invention as a dopant in        the light-emitting layer exhibit high external quantum        efficiency of electroluminescence;    -   3) The hole injection layer and the light-emitting layer of the        organic light emitting diodes are fabricated through orthogonal        solution process in the present invention, which can        significantly reduce device preparation costs;    -   4) The ligands of the phosphorescent complexes of the present        invention have meso/racemic configurations, the        electroluminescent emission changes from sky blue to orange red,        and the luminous efficiency of each color is relatively high.

DESCRIPTION OF THE DRAWING

FIG. 1 shows the schematic representation of the devices and thechemical structures of organic materials.

EXAMPLES

Hereinafter, the present invention will be further illustrated in moredetail below with reference to the accompanying drawings and theexamples to make the objects, technical solutions and technical effectsclearer. It is to be understood that the examples described in thedescription are only illustrative of the present invention and are notintended to limit the present invention.

In the following examples, dpmppe stands for (PPh₂CH₂PPhCH₂—)₂, carbstands for carbazolyl, PhBu^(t)-4 stands for 4-tert-butyl-phenyl,9-Ph-carb-3 stands for 9-phenyl-carbazol-3-yl, 9-Et-carb-3 stands for9-ethyl-carbazol-3-yl, PhCF₃-4 stands for 4-trifluoromethyl-phenyl,9-(4-Ph)-carb stands for 9-(4-phenyl)-carbazolyl, 10-Et-PTZ-3 stands for10-ethyl-phenothiazin-3-yl, and tht is tetrahydrothiophene.

Example 1: Preparation of[PtAg₂(rac-dpmppe)(C≡CC₆H₄Bu^(t)-4)₂{PhP(9-Ph-carb-3)₂}₂] (ClO₄)₂(rac-1) Complex

To a dichloromethane solution (20 mL) of Pt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂(80.6 mg, 0.078 mmol) was added rac-dpmppe (50 mg, 0.078 mmol). Afterbeing stirred for 30 minutes, concentrated and added with 20 mL ofhexane, a pale yellow solid was precipitated as an intermediate with ayield of 90% (80.8 mg). To a dichloromethane solution (20 mL) of theabove intermediate were added Ag(tht)ClO₄ (41.4 mg, 0.14 mmol) andPhP(9-Ph-carb-3)₂ (82.9 mg, 0.14 mmol). After being stirred for 1 hourat room temperature, the reaction solution turned pale green. Theproduct was purified by silica gel column chromatography usingCH₂Cl₂:MeCN (8:1) as eluent, and the pale green product was collected.Yield: 70%. Elemental analysis (C₁₄₈H₁₂₂Ag₂Cl₂N₄O₈P₆Pt), calculated: C,64.59; H, 4.47; N, 2.04. Found: C, 64.40; H, 4.55; N, 1.96. ESI-MS m/z(%): 1276.2909 (100) [M-2ClO₄]²⁺. ¹H-NMR (CDCl₃, ppm): 8.20-8.14 (dd,4H, J₁=16 Hz, J₂=12 Hz), 8.08-8.04 (dd, 4H, J₁=12 Hz, J₂=8 Hz),7.73-7.59 (m, 12H), 7.53-7.35 (m, 36H), 7.27-7.11 (m, 20H), 6.95-6.88(m, 12H), 6.69-6.67 (d, 4H, J=8 Hz), 6.59-6.57 (d, 4H, J=8 Hz), 4.29 (m,2H), 3.02-2.93 (3, 2H), 2.63-2.46 (m, 2H), 0.97 (s, 18H), 0.54 (m, 2H).³¹P-NMR (CDCl₃, ppm): 46.0 (d, 2P, J_(P—P)=78 Hz, J_(Pt—P)=2448 Hz),13.8 (m, 2P, J_(P—Ag)=526 Hz), 1.8 (m, 2P, J_(P—Ag)=526 Hz, J_(P—P)=52Hz). IR (KBr, cm⁻¹): 2081w (C≡C), 1099s (ClO₄ ⁻).

Example 2: Preparation of[PtAg₂(rac-dpmppe){(C≡C-4)C₆H₄-carb-9}₂(PPh₃)₂](ClO₄)₂ (rac-2) Complex

The preparation method was basically the same as that in Example 1,except that Pt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂ was replaced byPt(PPh₃)₂{(C≡C-4)C₆H₄-carb-9}₂, and PhP(9-Ph-carb-3)₂ was replaced byPPh₃. Yield: 71%. Elemental analysis (C₁₁₆H₉₂Ag₂Cl₂N₂O₈P₆Pt),calculated: C, 60.33; H, 4.02; N, 1.21. Found: C, 60.12; H, 4.02; N,1.15. ESI-MS m/z (%): 1055.1713 (100%, [M-2ClO₄]²⁺). ¹H-NMR (CDCl₃,ppm): 8.21-8.13 (m, 8H), 7.59-7.54 (m, 14H), 7.48-7.14 (m, 18H),7.34-7.24 (m, 22H), 7.20-7.12 (m, 14H), 7.02-6.98 (m, 4H), 6.86-6.85 (d,4H, J=7 Hz), 4.59 (m, 2H), 3.15-3.06 (m, 2H), 2.73-2.59 (m, 2H), 0.61(m, 2H). ³¹P-NMR (CDCl₃, ppm): 47.0 (d, 2P, J_(P—P)=76 Hz, J_(Pt—P)=2375Hz), 11.8 (m, 2P, J_(P—Ag)=506 Hz), 3.4 (m, 2P, J_(P—Ag)=410 Hz,J_(P—P)=45 Hz). IR (KBr, cm⁻¹): 2091w (C≡C), 1099s (ClO₄ ⁻).

Example 3: Preparation of[PtAg₂(rac-dpmppe){C≡C-(9-Ph-carb-3)}₂(PPh₃)₂](ClO₄)₂ (rac-3) Complex

The preparation method was basically the same as that in Example 1,except that Pt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂ was replaced byPt(PPh₃)₂(C≡C-(9-Ph-carb-3))₂, and PhP(9-Ph-carb-3)₂ was replaced byPPh₃. Yield: 71%. Elemental analysis (C₁₁₆H₉₂Ag₂Cl₂N₂O₈P₆Pt),calculated: C, 60.33; H, 4.02; N, 1.21. Found: C, 60.10; H, 4.05; N,1.16. ESI-MS m/z (%): 1055.1717 (100%, [M-2ClO₄]²⁺). ¹H-NMR (CDCl₃,ppm): 8.17-8.12 (dd, 4H, J₁=12 Hz, J₂=8 Hz), 7.67-7.63 (t, 4H, J=8 Hz),7.54-7.46 (m, 22H), 7.43-7.40 (m, 8H), 7.37-7.31 (m, 10H), 7.29-7.18 (m,10H), 7.13-7.03 (m, 20H), 6.95-6.92 (m, 4H), 6.83-6.81 (d, 2H), 4.45 (m,2H), 3.18-3.09 (m, 2H), 2.69-2.50 (m, 2H), 0.59 (m, 2H). ³¹P-NMR (CDCl₃,ppm): 46.3 (d, 2P, J_(P—P)=75 Hz, J_(Pt—P)=2384 Hz), 11.9 (m, 2P,J_(P—Ag)=510 Hz), 2.4 (m, 2P, J_(P—Ag)=398 Hz, J_(P—P)=51 Hz). IR (KBr,cm⁻¹): 2075w (C≡C), 1093s (ClO₄ ⁻).

Example 4: Preparation of[PtAg₂(rac-dpmppe)(C≡C-(9-Ph-carb-3))₂{P(9-Et-carb-3)₃}₂](ClO₄)₂ (rac-4)Complex

The preparation method was basically the same as that in Example 1,except that Pt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂ was replaced byPt(PPh₃)₂{C≡C-(9-Ph-carb-3)}₂, and PhP(9-Ph-carb-3)₂ was replaced byP(9-Et-carb-3)₃. Yield: 71%. Elemental analysis(C₁₆₄H₁₃₄Ag₂Cl₂N₈O₈P₆Pt), calculated: C, 65.39; H, 4.48; N, 3.72. Found:C, 65.14; H, 4.53; N, 3.53. ESI-MS m/z (%): 1406.8446 [M-2ClO₄]²⁺.¹H-NMR (CDCl₃, ppm): 8.27-8.22 (dd, 4H, J₁=12 Hz, J₂=8 Hz), 8.20-8.17(d, 6H, J=12 Hz), 8.04-7.99 (dd, 6H, J₁=12 Hz, J₂=8 Hz), 7.71 (s, 2H),7.50-7.40 (m, 16H), 7.37-7.32 (m, 12H), 7.27-7.25 (m, 10H), 7.17-7.14(m, 6H), 7.07-7.03 (t, 2H, J=7 Hz), 7.0-6.90 (m, 12H), 6.88-6.77 (m,16H), 6.73-6.66 (m, 4H), 4.4 (m, 2H), 3.88-3.83 (q, 12H, J=7 Hz),3.27-3.18 (m, 2H), 2.62-2.44 (m, 2H), 1.0-0.97 (d, 18H, J=7 Hz), 0.72(m, 2H). ³¹P-NMR (CDCl₃, ppm): 46.5 (d, 2P, J_(P—P)=78 Hz, J_(Pt—P)=2380Hz), 15.3 (m, 2P, J_(P—Ag)=534 Hz), 0.8 (m, 2P, J_(P—Ag)=378 Hz,J_(P—P)=53 Hz). IR (KBr, cm⁻¹): 2081w (C≡C), 1093s (ClO₄ ⁻).

Example 5: Preparation of[PtAg₂(rac-dpmppe){C≡C-(9-Et-carb-3)}₂{P(9-Et-carb-3)₃}₂] (ClO₄)₂(rac-5) Complex

The preparation method was basically the same as that in Example 1,except that Pt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂ was replaced byPt(PPh₃)₂{C≡C-(9-Et-carb-3)}₂, and PhP(9-Ph-carb-3)₂ was replaced byP(9-Et-carb-3)₃. Yield: 72%. Elemental analysis(C₁₅₆H₁₃₄Ag₂Cl₂N₈O₈P₆Pt), calculated: C, 64.25; H, 4.63; N, 3.84. Found:C, 64.02; H, 4.65; N, 3.58. ESI-MS m/z (%): 1358.3459 (100%)[M-2ClO₄]²⁺. ¹H-NMR (CDCl₃, ppm): 8.25-8.16 (m, 8H), 8.01 (m, 6H),7.73-7.68 (m, 10H), 7.44-7.27 (m, 28H), 7.18-7.02 (m, 10H), 6.94-6.82(m, 22H), 6.70-6.64 (m, 4H), 4.33 (m, 2H), 4.05-3.99 (q, 4H, J=7 Hz),3.85-3.79 (q, 12H, J=7 Hz), 3.26-3.22 (m, 2H), 2.64-2.51 (m, 2H),1.29-1.15 (t, 6H, J=7 Hz), 1.11-0.97 (t, 18H, J=7 Hz), 0.71 (m, 2H).³¹P-NMR (CDCl₃, ppm): 46.2 (d, 2P, J_(P—P)=78 Hz, J_(Pt—P)=2376 Hz),15.3 (m, 2P, J_(P—Ag)=524 Hz), 0.6 (m, 2P, J_(P—Ag)=369 Hz, J_(P—P)=52Hz). IR (KBr, cm⁻¹): 2073w (C≡C), 1093s (ClO₄ ⁻).

Example 6: Preparation of[PtAg₂(rac-dpmppe){C≡C-(10-Et-PTZ-3)}₂{P(9-Et-carb-3)₃}₂] (ClO₄)₂(rac-6) Complex

The preparation method was basically the same as that in Example 1,except that Pt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂ was replaced byPt(PPh₃)₂{C≡C-(10-Et-PTZ-3)}₂, and PhP(9-Ph-carb-3)₂ was replaced byP(9-Et-carb-3)₃. Yield: 73%. Elemental analysis(C₁₅₆H₁₃₄Ag₂Cl₂N₈O₈P₆PtS₂), calculated: C, 62.86; H, 4.53; N, 3.76.Found: C, 62.62; H, 4.57; N, 3.59. ESI-MS m/z (%): 1390.8150 (100%)[M-2ClO₄]²⁺. ¹H-NMR (CDCl₃, ppm): 8.16-8.13 (m, 8H), 8.01-7.96 (dd, 6H,J=8 Hz), 7.58-7.55 (m, 6H), 7.42-7.38 (m, 12H), 7.34-7.30 (m, 8H),7.15-6.99 (m, 22H), 6.90-6.86 (m, 14H), 6.69-6.67 (d, 2H, J=8 Hz),6.54-6.52 (d, 2H, J=8 Hz), 6.35-6.32 (m, 4H), 5.92-5.90 (d, 2H, J=8 Hz),4.23 (m, 2H), 4.05-3.99 (q, 12H, J=7 Hz), 3.45-3.39 (q, 4H, J=7 Hz),3.06-2.97 (m, 2H), 2.64-2.45 (m, 2H), 1.18-1.14 (t, 18H, J=7 Hz),1.06-1.02 (t, 6H, J=7 Hz), 0.59 (m, 2H). ³¹P-NMR (CDCl₃, ppm): 46.5 (d,2P, J_(P—P)=78 Hz, J_(Pt—P)=2376 Hz), 15.2 (m, 2P, J_(P—Ag)=536 Hz), 1.5(m, 2P, J_(P—Ag)=381 Hz, J_(P—P)=54 Hz). IR (KBr, cm⁻¹): 2081w (C≡C),1093s (ClO₄ ⁻).

Example 7: Preparation of[PtAg₂(meso-dpmppe)(C≡CC₆H₄CF₃-4)₂(PPh₃)Cl](ClO₄) (meso-7) Complex

To a dichloromethane solution (20 mL) of Pt(PPh₃)₂(C≡CC₆H₄CF₃-4)₂ (82.5mg, 0.078 mmol) was added meso-dpmppe (50 mg, 0.078 mmol). After beingstirred for 30 minutes, concentrated and added with 20 mL of hexane, apale yellow solid was precipitated as an intermediate with a yield of90% (82.4 mg). PPh₃ (18.3 mg, 0.07 mmol) and ^(n)Bu₄NCl (19.5 mg, 0.07mmol) were firstly mixed. To a dichloromethane solution (20 mL) of theabove intermediate were added the mixed solution and Ag(tht)ClO₄ (41.4mg, 0.14 mmol). After being stirred for 1 hour at room temperature, thereaction solution turned pale blue. The product was purified by silicagel column chromatography using CH₂Cl₂:MeCN (15:1) as eluent, and thepale yellow product was collected. Yield: 75%. Elemental analysis(C₇₆H₆₁Ag₂Cl₂F₆O₄P₅Pt), calculated: C, 51.03; H, 3.44. Found: C, 51.21;H, 3.60. ESI-MS m/z (%): 1688.0808 (100%, [M-ClO₄]⁺). ¹H-NMR (CDCl₃,ppm): 8.03-7.96 (m, 8H), 7.59-7.36 (m, 22H), 7.33-7.29 (t, 4H, J=7 Hz),7.25-7.17 (m, 11H), 6.92-6.89 (m, 4H), 6.65-6.62 (m, 4H), 3.86 (m, 2H),3.37 (m, 2H), 2.28-2.11 (m, 4H). ³¹P-NMR (CDCl₃, ppm): 47.6 (dd, 2P,J_(P—P)=30 Hz, J_(Pt—P)=2412 Hz), 7.6 (m, 1P, J_(P—Ag)=579 Hz), −8.9 (m,2P, J_(P—Ag)=422 Hz, J_(P—P)=59 Hz). IR (KBr, cm⁻¹): 2092w (C≡C), 1104s(ClO₄ ⁻).

Example 8: Preparation of[PtAg₂(meso-dpmppe)(C≡CC₆H₄Bu^(t)-4)₂(PPh₃)Cl](ClO₄) (meso-8) Complex

The preparation method was basically the same as that in Example 7,except that Pt(PPh₃)₂(C≡CC₆H₄CF₃-4)₂ was replaced byPt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂. Yield: 74%. Elemental analysis(C₈₂H₇₉Ag₂Cl₂O₄P₅Pt), calculated: C, 55.80; H, 4.51. Found: C, 56.02; H,4.74. ESI-MS m/z (%): 1665.2304 (100%, [M-ClO₄]⁺). ¹H-NMR (CDCl₃, ppm):8.03-7.97 (m, 8H), 7.53-7.50 (m, 7H), 7.41-7.31 (m, 20H), 7.24-7.16 (m,12H), 6.71-6.59 (m, 8H), 3.81 (m, 2H), 3.46 (m, 2H), 2.18-2.01 (m, 4H),1.45 (s, 18H). ³¹P-NMR (CDCl₃, ppm): 47.1 (q, 2P, J_(P—P)=30 Hz,J_(Pt—P)=2409 Hz), 7.2 (m, 1P, J_(P—Ag)=565 Hz), −9.5 (m, 2P,J_(P—Ag)=417 Hz, J_(P—P)=58 Hz). IR (KBr, cm⁻¹): 2092w (C≡C), 1093s(ClO₄ ⁻).

Example 9: Preparation of[PtAg₂(meso-dpmppe)(C≡CC₆H₄Bu^(t)-4)₂{P(9-Et-carb-3)₃}Cl] (ClO₄)(meso-9) Complex

The preparation method was basically the same as that in Example 7,except that Pt(PPh₃)₂(C≡CC₆H₄CF₃-4)₂ was replaced byPt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂, and PPh₃ was replaced by P(9-Et-carb-3)₃.Yield: 74%. Elemental analysis (C₁₀₆H₁₀₀Ag₂Cl₂N₃O₄P₅Pt), calculated: C,60.15; H, 4.76; N, 1.99. Found: C, 60.32; H, 4.73; N, 1.88. ESI-MS m/z(%): 2016.4011 (100%, [M-ClO₄]⁺). ¹H-NMR (CDCl₃, ppm): 8.48-8.45 (d, 2H,J=12 Hz), 8.08-8.04 (dd, 4H, J₁=12 Hz, J₂=8 Hz), 7.94-7.92 (d, 2H, J=8Hz), 7.89 (m, 4H), 7.53-7.41 (m, 26H), 7.25-7.15 (m, 13H), 6.61-6.59 (m,4H), 6.40-6.38 (m, 4H), 4.41-4.37 (q, 6H, J=7 Hz), 3.76 (m, 2H), 3.49(m, 2H), 2.24-2.05 (m, 4H), 1.49-1.47 (t, 9H, J=7 Hz), 0.76 (s, 18H).³¹P-NMR (CDCl₃, ppm): 47.5 (q, 2P, J_(P—P)=29 Hz, J_(Pt—P)=2394 Hz),10.4 (m, 1P, J_(P—Ag)=601 Hz), −9.3 (m, 2P, J_(P—Ag)=417 Hz, J_(P—P)=56Hz). IR (KBr, cm⁻¹): 2110w (C≡C), 1093s (ClO₄ ⁻).

Example 10: Preparation of[PtAg₂(meso-dpmppe)(C≡CC₆H₄Bu^(t)-4)₂{P(9-Et-carb-3)₃}I] (ClO₄)(meso-10) Complex

The preparation method was basically the same as that in Example 7,except that Pt(PPh₃)₂(C≡CC₆H₄CF₃-4)₂ was replaced byPt(PPh₃)₂(C≡CC₆H₄Bu^(t)-4)₂, PPh₃ was replaced by P(9-Et-carb-3)₃, and^(n)Bu₄NCl was replaced by ^(n)Bu₄NI. Yield: 72%. Elemental analysis(C₁₀₆H₁₀₀Ag₂ClIN₃O₄P₅Pt), calculated: C, 57.66; H, 4.56; N, 1.90. Found:C, 57.57; H, 4.60; N, 1.83. ESI-MS m/z (%): 2108.3387 (100%, [M-ClO₄]⁺).¹H-NMR (CDCl₃, ppm): 8.51-8.48 (d, 2H, J=12 Hz), 8.11-8.07 (dd, 4H,J₁=12 Hz, J₂=8 Hz), 7.98-7.96 (d, 2H, J=8 Hz), 7.82 (m, 4H), 7.54-7.40(m, 26H), 7.29-7.16 (m, 13H), 6.54-6.52 (m, 4H), 6.37-6.35 (m, 4H),4.39-4.35 (q, 6H, J=7 Hz), 3.71 (m, 2H), 3.52 (m, 2H), 2.25-2.05 (m,4H), 1.49-1.47 (t, 9H, J=7 Hz), 0.72 (s, 18H). ³¹P-NMR (CDCl₃, ppm):48.5 (q, 2P, J_(P—P)=30 Hz, J_(Pt—P)=2391 Hz), 9.0 (m, 1P, J_(P—Ag)=547Hz), −11.7 (m, 2P, J_(P—Ag)=386 Hz, J_(P—P)=59 Hz). IR (KBr, cm⁻¹):2104w (C≡C), 1093s (ClO₄ ⁻).

Example 11: Preparation of [PtAg₂(meso-dpmppe)(C≡C-(10-Et-PTZ-3))₂{P(9-Et-carb-3)₃}(μ-I)](ClO₄) (meso-11) Complex

The preparation method was basically the same as that in Example 7,except that Pt(PPh₃)₂(C≡CC₆H₄CF₃-4)₂ was replaced byPt(PPh₃)₂{C≡C-(10-Et-PTZ-3)}₂, PPh₃ was replaced by P(9-Et-carb-3)₃, and^(n)Bu₄NCl was replaced by ^(n)Bu₄NI. Yield: 75%. Elemental analysis(C₁₁₄H₉₈Ag₂ClIN₅O₄P₅PtS₂), calculated: C, 57.19; H, 4.13; N, 2.93.Found: C, 57.42; H, 4.33; N, 2.84. ESI-MS m/z (%): 2294.2671 (100%,[M-ClO₄]⁺). ¹H-NMR (CDCl₃, ppm): 8.54-8.51 (d, 2H, J=12 Hz), 8.09-8.04(dd, 4H, J₁=12 Hz, J₂=8 Hz), 7.95-7.93 (d, 2H, J=8 Hz), 7.80 (m, 4H),7.59-7.29 (m, 29H), 7.18-7.01 (m, 12H), 6.75 (m, 4H), 6.51-6.49 (d, 2H,J=8 Hz), 6.41-6.39 (d, 2H, J=8 Hz), 6.22 (s, 2H), 5.63-5.61 (d, 2H, J=8Hz), 4.45-4.27 (q, 6H, J=7 Hz), 3.71 (m, 2H), 3.46 (m, 2H), 3.14-3.08(q, 4H, J=6 Hz), 2.28-2.03 (m, 4H), 1.44-1.40 (t, 9H, J=7 Hz), 0.86-0.81(t, 6H, J=6 Hz). ³¹P-NMR (CDCl₃, ppm): 48.6 (q, 2P, J_(P—P)=29 Hz,J_(Pt—P)=2391 Hz), 9.1 (m, 1P, J_(P—Ag)=548 Hz), −11.4 (m, 2P,J_(P—Ag)=384 Hz, J_(P—P)=60 Hz). IR (KBr, cm⁻¹): 2101w (C≡C), 1094s(ClO₄ ⁻).

Example 12: Photoluminescence Performance Measurement

The excitation spectra, emission spectra, luminescence lifetimes andluminescence quantum yields of the complex rac-1, rac-4, rac-5, rac-6prepared in Examples 1, 4, 5 and 6 in solid powder and in the thin filmof 70.5% 2,6-DCZPPY:23.5% OXD-7:6% of the complex rac-1, rac-4, rac-5and rac-6 of the present invention (by weight), and the complex meso-11prepared in Example 11 in solid powder and in the thin film of 90%2,6-DCZPPY:10% of the complex meso-11 of the present invention (byweight) were measured on Edinburgh FLS920 fluorescence spectrometer,respectively. The luminescence quantum yields of the solid powdersamples were determined by using a 142-mm-diameter integrating sphere.

The emission wavelengths and quantum yields of the complexes rac-1,rac-4, rac-5, rac-6 and meso-11 in solid state were 500 nm and 15.1%(rac-1), 566 nm and 37.1% (rac-4), 580 nm and 30.4% (rac-5), 662 nm and1.7% (rac-6) and 600 nm and 8.1% (meso-11), respectively;

The emission wavelengths and quantum yields of the complexes rac-1,rac-4, rac-5 and rac-6 in the thin film of 70.5% 2,6-DCZPPY:23.5%OXD-7:6% of the complexes rac-1, rac-4, rac-5 and rac-6 of the presentinvention (by weight) were 487 nm and 52.2% (rac-1), 527 nm and 90.5%(rac-4), 535 nm and 77.0% (rac-5), 616 nm and 56.8% (rac-6),respectively; the emission wavelength and quantum yield of the complexmeso-11 in the thin film of 90% 2,6-DCZPPY: 10% of the complex meso-11of the present invention (by weight) were 570 nm and 52.2% (meso-11).

Example 13: Fabrication of Organic Light Emitting Diodes andElectroluminescence Performance Measurement

The organic light emitting diode was prepared with a light-emittinglayer by doping the blended host materials of 2,6-DCZPPY (70.5%):OXD-7(23.5%) with 6 wt % of the phosporescent complex rac-1, rac-4, rac-5, orrac-6 prepared in Example 1, 4, 5, or 6 as a luminescent material,respectively. The device structure was ITO/PEDOT:PSS (50 nm)/CuSCN (30nm)/70.5% 2,6-DCZPPY:23.5% OXD-7:6 wt % of the complex rac-1, rac-4,rac-5, or rac-6 of the invention (50 nm)/BmPyPB (50 nm)/LiF (1 nm)/Al(100 nm); the organic light emitting diode was prepared with alight-emitting layer by doping the host materials of 2,6-DCZPPY (90%)with 10 wt % of the phosporescent complex meso-11 prepared in Example 11as a luminescent material. The device structure was ITO/PEDOT:PSS (50nm)/CuSCN (30 nm)/90% 2,6-DCZPPY:10 wt % of the complex meso-11 of thepresent invention (50 nm)/BmPyPB (50 nm)/LiF (1 nm)/Al (100 nm).

Firstly, an ITO substrate was cleaned with deionized water, acetone andisopropanol, respectively, followed by UV-ozone treatment for 15minutes. The filtered aqueous solution of PEDOT:PSS was spin coated ontothe ITO substrate at 4800 rpm, dried at 140° C. for 20 minutes to afforda 50-nm-thick hole injection layer. And then a solution of CuSCN indiethyl sulfide (10 mg/mL) was spin coated at 4800 rpm onto thePEDOT:PSS hole injection layer, dried at 120° C. for 30 minutes toafford a 30-nm-thick hole transport layer. Secondly, the filteredsolution of 70.5% 2,6-DCZPPY:23.5% OXD-7:6% the complex rac-1, rac-4,rac-5, or rac-6 of the present invention (percentage by weight) indiethyl sulfide (5.5 mg/mL), or a solution of 90% 2,6-DCZPPY:10% thecomplex meso-11 of the present invention (percentage by weight) indiethyl sulfide (5.5 mg/mL) was spin coated at 2100 rpm onto thePEDOT:PSS thin film to form a 50-nm-thick light-emitting layer. Afterthat, the ITO substrate was loaded into a vacuum deposition chamber witha pressure of less than 4×10⁻⁴ Pa, and subsequently thermally depositedwith a 50-nm-thick BmPyPB layer, a 1-nm-thick LiF electron injectionlayer, and 100-nm-thick Al as a cathode of the device.

The LED device performance was determined at room temperature in dryambient air. The parameters of the electroluminescence performance,including electroluminescence emission wavelength (λ_(EL)), turn-onvoltage (V_(on)), maximum luminance (L_(max)), maximum currentefficiency (CE_(max)), maximum power efficiency (PE_(max)), and maximumexternal quantum efficiency (EQE_(max)), are listed in Table 1.

TABLE 1 Electroluminescence performance data of the phosphorescentcomplex rac-1, rac-4, rac-5, rac-6 or meso-11 of the invention L_(max)Com- λ_(EL) V_(on) [cd/ CE_(max) PE_(max) EQE_(max) plex [nm] [V]^(a))m²]^(b)) [cd/A]^(c)) [lm/W]^(d)) [%]^(e)) CIE^(f)) rac-1 486 4.8 170327.20 13.25 11.1 0.19, 0.24 rac-4 527 4.8 7764 60.96 30.89 18.1 0.24,0.48 rac-5 537 4.7 6652 57.00 28.70 16.6 0.28, 0.53 rac-6 616 4.6 189819.84 9.89 12.4 0.53, 0.46 meso- 572 3.9 2336 30.65 18.68 10.4 0.41,0.54 11 ^(a))turn-on voltage at luminance of 1 cd/m², ^(b))maximumluminance, ^(c))maximum current efficiency, ^(d))maximum powerefficiency, ^(e))maximum external quantum efficiency, ^(f))chromaticitycoordinates.

1. An ionic-type phosphorescent metal complex having a structure asshown in the following formula (I) or formula (II):[PtAg₂{rac-(PPh₂CH₂PPhCH₂—)₂}(C≡CR)₂(PR′₃)₂]²⁺A^(n−) _(2/n);  (I)or[PtAg₂{meso-(PPh₂CH₂PPhCH₂—)₂}(C≡CR)₂(PR′₃)(μ-X)]⁺ _(m)A^(m−)  (II)wherein, R is identical or different, independently selected from alkyl,aryl, heteroaryl or heteroaryl aryl; R′ is identical or different,independently selected from alkyl, aryl or heteroaryl; the alkyl, thearyl or the heteroaryl is optionally substituted by one or moresubstituents, and the substituents are selected from an alkyl group, analkenyl group, an alkynyl group, an alkoxy group, an amino group, ahalogen, a haloalkyl group and an aryl group; X is halogen; A^(m−) orA^(n−) is a monovalent or bivalent anion, and m or n is 1 or 2; theanion is, for example, ClO₄ ⁻, PF₆ ⁻, SbF₆ ⁻, BF₄ ⁻, SiF₆ ²⁻, etc; μstands for bridging.
 2. The phosphorescent metal complex according toclaim 1, wherein a stereostructure of the phosphorescent metal complexof formula (I) or formula (II) is represented as follows:


3. The phosphorescent metal complex according to claim 1, wherein R isaryl, carbazolyl, phenothiazinyl or carbazolylaryl; the aryl, thecarbazolyl or the phenothiazinyl is optionally substituted by one ormore substituents, and the substituents are selected from the groupconsisting of alkyl, alkoxy, amino, halogen, haloalkyl and aryl; R′ isaryl, or nitrogen-containing heterocyclic; the aryl, ornitrogen-containing heterocyclic is optionally substituted by one ormore substituents, and the substituents are selected from the groupconsisting of alkyl, alkoxy, amino, halogen, haloalkyl, aryl; morepreferably, R is phenyl, alkylphenyl, haloalkylphenyl, carbazolylphenyl,carbazolyl, alkylcarbazolyl, phenylcarbazolyl, phenothiazinyl oralkylphenothiazinyl; R′ is phenyl, alkylphenyl, carbazolyl,alkylcarbazolyl or phenylcarbazolyl.
 4. The phosphorescent metal complexaccording to claim 1, wherein the metal complex is specifically selectedfrom the following 11 complexes:


5. A method for preparing the phosphorescent metal complex according toclaim 1, wherein the preparation method of the phosphorescent metalcomplex of formula (I) comprises the following steps: 1) reactingrac-(PPh₂CH₂PPhCH₂—)₂ with Pt(PPh₃)₂(C≡CR)₂ in a solvent to obtain anintermediate; 2) the intermediate obtained in step 1) further reactingwith [Ag(tht)](A^(n−)) and PR′₃ in a solvent to obtain thephosphorescent complex of formula (I), wherein the tht istetrahydrothiophene, and the A^(n−), R, R′ and X are as definedaccording to claim 1; Or, the preparation method of the phosphorescentcomplex of formula (II) comprises the following steps: A) reactingmeso-(PPh₂CH₂PPhCH₂—)₂ with Pt(PPh₃)₂(C≡CR)₂ in a solvent to obtain anintermediate; B) the intermediate obtained in step A) further reactingwith PR′₃, ^(n)Bu₄NX and [Ag(tht)](A^(m−)) in a solvent to obtain thephosphorescent complex of formula (II), wherein the tht istetrahydrothiophene, and the A^(m−), R, R′ and X are as definedaccording to claim
 1. 6. Use of the phosphorescent complex according toclaim 1 in organic light emitting diodes.
 7. An organic light emittingdiode, comprising a light-emitting layer, wherein the light-emittinglayer comprises the phosphorescent complex of formula (I) or formula(II) according to claim 1; preferably, in the light-emitting layer, thephosphorescent complex of formula (I) according to claim 1 accounts for3-20% (percentage by weight) of all materials; the phosphorescentcomplex of formula (II) according to claim 1 accounts for 5-25%(percentage by weight) of all materials.
 8. The organic light emittingdiode according to claim 7, wherein the organic light emitting diodefurther comprises an anode layer, a hole injection layer, optionally ahole transport layer, a light-emitting layer, an electron transportlayer, an electron injection layer and a cathode layer.
 9. The organiclight emitting diode according to claim 8, wherein the anode is indiumtin oxide, and the hole injection layer is PEDOT:PSS(PEDOT:PSS=poly(3,4-ethyleneoxythiophene)-poly(styrene sulfonate)); thehole transport layer is CuSCN, CuI or CuBr; the light-emitting layercomprises the phosphorescent complex according to claim 1 and asubstance having a hole-transport and/or electron-transport property;the electron transport layer is one or more selected from BmPyPB (3,3″,5,5″-tetra(pyridin-3-yl)-1,1′:3′,1″-terphenyl), TPBi(1,3,5-tris(1-phenyl-1H-benzo[d]imidazole-2-yl)phenyl), BCP(2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) or OXD-7; the electroninjection layer is LiF, and the cathode layer is Al; preferably, adevice structure containing the phosphorescent complex of formula (I) isITO/PEDOT:PSS/CuSCN/70.5% 2,6-DCZPPY:23.5% OXD-7:6 wt % of the complexof formula (I) according to claim 1/BmPyPB/LiF/Al, orITO/PEDOT:PSS/70.5% mCP:23.5% OXD-7:6 wt % of the complex of formula (I)according to claim 1/BmPyPB/LiF/Al; a device structure containing thephosphorescent complex of formula (II) is ITO/PEDOT:PSS/CuSCN/90%2,6-DCZPPY:10 wt % of the complex of formula (II) according to claim1/BmPyPB/LiF/Al, or ITO/PEDOT:PSS/90% mCP:10 wt % of the complex offormula (II) according to claim 1/BmPyPB/LiF/Al; wherein ITO is anindium tin oxide conductive film, PEDOT:PSS ispoly(3,4-ethyleneoxythiophene)-poly(styrene sulfonate), 2,6-DCZPPY is2,6-bis (3-(9H-carbazol-9-yl)phenyl)pyridine, mCP is1,3-bis(9-carbazolyl)benzene, OXD-7 is1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene and BmPyPBis 3,3″, 5,5″-tetra(pyridin-3-yl)-1,1′:3′,1″-terphenyl.
 10. Use of theorganic light emitting diode according to claim 7, which is used in thefield of flat-panel displays and daily lighting.